EP0707085B1 - Körperverträgliche Legierung auf Titan-Basis mit niedrigen Modul für medezinische Geräte - Google Patents
Körperverträgliche Legierung auf Titan-Basis mit niedrigen Modul für medezinische Geräte Download PDFInfo
- Publication number
- EP0707085B1 EP0707085B1 EP95307277A EP95307277A EP0707085B1 EP 0707085 B1 EP0707085 B1 EP 0707085B1 EP 95307277 A EP95307277 A EP 95307277A EP 95307277 A EP95307277 A EP 95307277A EP 0707085 B1 EP0707085 B1 EP 0707085B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- medical device
- alloys
- weight
- atomic percent
- elasticity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00011—Metals or alloys
- A61F2310/00023—Titanium or titanium-based alloys, e.g. Ti-Ni alloys
Definitions
- the present invention relates to biocompatible titanium base alloys which exhibit a low modulus of elasticity.
- the invention relates to biocompatible titanium base alloys with niobium, tantalum, and zirconium in such relative proportions that the resulting alloys are ductile and exhibit a stable beta (BCC) morphology, a modulus of elasticity below 70 GPa, and a tensile strength of at least 550 MPa (80,000 psi).
- This invention relates to a family of quaternary titanium base alloys, which are composed of biocompatible elements and are free from toxic metallic elements such as Al, Fe, Ni, Co, Cr, Mo, or W, and are therefore useful in medical devices which are intended to reside on or in the human body for an extended period of time.
- One such device is a surgical implant, and for the purpose of illustration, the invention will be described for such a use, although it is to be understood that the alloys may have other utility, both medical and non-medical, by virtue of their chemical and physical properties.
- the alloys be free of elements which are toxic to human beings, and be composed entirely of elements which are biocompatible with human tissues. It is also desirable that the alloys are ductile and possess a low modulus of elasticity comparable to that of bones in the human body.
- Biocompatible titanium base alloys are described in a number of United States Patents including the following:
- the present invention is an improvement over the alloys described in the above noted patents insofar as it provides novel fully biocompatible alloys with a low modulus of elasticity.
- the toxicity of various elements are discussed and alloys of titanium and/or zirconium containing 3 to 30% by weight of at least one member selected from the group consisting of Nb, Ta, Cr, Mo, and Al are described.
- Several ⁇ - ⁇ alloys are described along with a number of alloys containing Al, Mo, and Cr. No quaternary alloys of Ti, Nb, Ta, and Zr are described.
- the presence of Al, Cr, or Mo is undesirable because of their toxicity when the alloys are utilized in medical devices, such as surgical implants.
- the alloys of the present invention do not contain any Al, Cr, or Mo.
- the alloys described in the two Wang et al patents contain an amount up to 3% of at least one eutectoid beta stabilizer selected from the group consisting of Fe, Mn, Cr, Co, and Ni, each of which is orders of magnitude more toxic than Ti, Zr, Nb, or Ta.
- the alloys described in these patents possess a modulus of elasticity (E) of 66.9 to 100 GPa with most of the alloys exhibiting a modulus of elasticity between 75 and 100 GPa.
- the alloys of the present invention do not contain any of the toxic eutectoid stabilizers required by Wang et al.
- One object of the present invention is to provide new and improved alloys for medical devices intended to remain on or in a living human body for an extended period of time.
- a further object is to provide new and improved biocompatible titanium base alloys which possess moduli of elasticity below 70 GPa, preferably 65 GPa, and most preferably between 50 and 60 GPa.
- Another object is to produce biocompatible titanium base alloys of Ti, Nb, Ta, and Zr exhibiting a modulus of elasticity below 70 GPa.
- a further object of the invention is to provide surgical implants composed of the novel alloys of this invention.
- Still a further object of the invention is to provide titanium base alloys consisting essentially of between about 2 and about 9 atomic percent Zr and between about 22 and 30 atomic percent of Nb plus Ta and the balance Ti, with the atomic ratio of Nb to Ta between 2 and 16. Stated in weight percent, the alloys of this invention comprise between about 2.5 up to 13% Zr, 20 to 40% Nb, 5 to 25% Ta, the total of Nb and Ta being between about 36.5 and 47%, the balance being Ti.
- a further object is to provide biocompatible ⁇ stable titanium base alloys of Ta, Nb, and Zr which are isotropic when solution annealed.
- a medical device for use in the human body having been fabricated from an isotropic, biocompatible titanium alloy consisting of between 2.5% and 13% by weight Zr, between 20% and 40% by weight Nb, between 4.5% and 25% Ta, and the balance Ti;
- the Nb plus Ta content of the alloy is preferably between 38% and 46% by weight.
- the Ti content of the alloy is preferably between 46% and 58% by weight.
- Tables 1 and 2 describe alloys of the present invention prepared from pure elemental metals which were melted in either an arc or plasma furnace to form the desired composition.
- the resulting ingot may be forged or machined to the shape of the device in which the alloy is to be used.
- Solution heat treatment to ensure an all ⁇ structure, or a combination of heat treatment and/or working may be employed to produce an ⁇ - ⁇ alloy if such is desired.
- the biocompatible titanium-zirconium-niobium-tantalum alloys of this invention may also include one or more non-toxic interstitial elements (C,N, and O) for the beneficial effects these elements have on the physical properties of the alloys.
- the total amounts of these elements which may be added to the alloys of this invention should not exceed 0.5% by weight.
- the drawing is a plot of moduli of elasticity for the titanium based alloys of Tables 1 and 2 with 2 to 9 atomic percent Zr, 22 to 27 atomic percent Ta plus Nb, and various atomic ratios of Nb/Ta between 1.9 and 16.
- the quaternary alloys of the present invention contain between 2 and 9 atomic percent Zr, Nb/Ta ratios from 1.9 to 16, and exhibit moduli of elasticity between 47.1 and 66.6 GPa.
- Particularly preferred alloys are those with the lowest moduli of elasticity, as shown on the graph.
- Three such preferred alloys described in the tables are TA5, TA7, and TA22 with the following compositions, in weight percent: 23.8 Nb 21.6 Ta 4.6 Zr balance Ti 29.2 Nb 12.4 Ta 7.1 Zr balance Ti 35.3 Nb 5.7 Ta 7.3 Zr balance Ti
- Implants fabricated from the alloys of this invention may be coated or given other surface treatments such as passivation to enhance their utility.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Inorganic Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Dermatology (AREA)
- Veterinary Medicine (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Claims (14)
- Medizinische Einrichtung zur Verwendung im menschlichen Körper, hergestellt aus einer isotropen, biokompatiblen Titanlegierung, bestehend aus zwischen 2,5 und 13 Gew.% Zr, zwischen 20 und 40 Gew.% Nb, zwischen 4,5 und 25 Gew.% Ta, wahlweise bis zu insgesamt 0,5 Gew.% mindestens eines Zwischengitterelements, ausgewählt aus der Gruppe C, N und 0, und einem Ausgleich Ti,
wobei das Gewicht von Nb und Ta zwischen 35 und 52% ist, das Atomverhältnis von Nb zu Ta zwischen 1,9 und 16 ist, und die relativen Anteile Ti, Zr, Ta und Nb so sind, dass der Elastizitätsmodul unter 70 GPa ist. - Medizinische Einrichtung nach Anspruch 1, wobei die Legierung besteht aus 29,2% Nb, 12,4% Ta, 7,1% Zr, bezogen auf das Gewicht, und einem Ausgleich Ti.
- Medizinische Einrichtung nach Anspruch 1, wobei die Legierung besteht aus 23,8% Nb, 21,6% Ta, 4,6% Zr, bezogen auf das Gewicht, und einem Ausgleich Ti.
- Medizinische Einrichtung nach Anspruch 1, wobei die Legierung besteht aus 35,3% Nb, 5,7% Ta, 7,3% Zr, bezogen auf das Gewicht, und einem Ausgleich Titan.
- Medizinische Einrichtung nach Anspruch 1, wobei der Gehalt an Nb und Ta zwischen 38 und 46 Gew.% ist.
- Medizinische Einrichtung nach Anspruch 1, wobei der Titangehalt zwischen 46 und 58 Gew.% ist.
- Medizinische Einrichtung nach irgendeinem Anspruch 1 bis 6, wobei die medizinische Einrichtung ein chirurgisches Implantat ist.
- Medizinische Einrichtung nach irgendeinem Anspruch 1 bis 6, wobei die medizinische Einrichtung ein Prothetik-Implantat ist.
- Medizinische Einrichtung nach Anspruch 1, wobei die Legierung besteht aus zwischen 2 und 9 Atomprozent Zr, zwischen 24 und 30 Atomprozent Nb und Ta und einem Ausgleich Titan.
- Medizinische Einrichtung nach irgendeinem Anspruch 1 bis 9, wobei die Legierung lösungsgetempert ist.
- Medizinische Einrichtung nach Anspruch 1, wobei der Zirkongehalt zwischen 4 und 7 Atomprozent ist, der Gehalt an Ta und Nb zwischen 22 und 28 Atomprozent ist und der Elastizitätsmodul unter 58 GPa ist.
- Medizinische Einrichtung nach Anspruch 1, wobei das Atomverhältnis von Nb zu Ta zwischen 4 und 6 ist.
- Medizinische Einrichtung nach Anspruch 1, wobei das Atomverhältnis von Nb zu Ta zwischen 10 und 14 ist.
- Medizinische Einrichtung nach irgendeinem Anspruch 1 bis 13, wobei der Elastizitätsmodul unter 57 GPa ist.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US32345394A | 1994-10-14 | 1994-10-14 | |
US323453 | 1994-10-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0707085A1 EP0707085A1 (de) | 1996-04-17 |
EP0707085B1 true EP0707085B1 (de) | 1999-01-07 |
Family
ID=23259264
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95307277A Expired - Lifetime EP0707085B1 (de) | 1994-10-14 | 1995-10-13 | Körperverträgliche Legierung auf Titan-Basis mit niedrigen Modul für medezinische Geräte |
Country Status (6)
Country | Link |
---|---|
US (1) | US5871595A (de) |
EP (1) | EP0707085B1 (de) |
JP (1) | JPH08299428A (de) |
AU (1) | AU705336B2 (de) |
CA (1) | CA2159974A1 (de) |
DE (1) | DE69507104T2 (de) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
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US7611592B2 (en) | 2006-02-23 | 2009-11-03 | Ati Properties, Inc. | Methods of beta processing titanium alloys |
US7837812B2 (en) | 2004-05-21 | 2010-11-23 | Ati Properties, Inc. | Metastable beta-titanium alloys and methods of processing the same by direct aging |
US8048240B2 (en) | 2003-05-09 | 2011-11-01 | Ati Properties, Inc. | Processing of titanium-aluminum-vanadium alloys and products made thereby |
US8337750B2 (en) | 2005-09-13 | 2012-12-25 | Ati Properties, Inc. | Titanium alloys including increased oxygen content and exhibiting improved mechanical properties |
US8499605B2 (en) | 2010-07-28 | 2013-08-06 | Ati Properties, Inc. | Hot stretch straightening of high strength α/β processed titanium |
US8652400B2 (en) | 2011-06-01 | 2014-02-18 | Ati Properties, Inc. | Thermo-mechanical processing of nickel-base alloys |
US9050647B2 (en) | 2013-03-15 | 2015-06-09 | Ati Properties, Inc. | Split-pass open-die forging for hard-to-forge, strain-path sensitive titanium-base and nickel-base alloys |
US9192981B2 (en) | 2013-03-11 | 2015-11-24 | Ati Properties, Inc. | Thermomechanical processing of high strength non-magnetic corrosion resistant material |
US9206497B2 (en) | 2010-09-15 | 2015-12-08 | Ati Properties, Inc. | Methods for processing titanium alloys |
US9255316B2 (en) | 2010-07-19 | 2016-02-09 | Ati Properties, Inc. | Processing of α+β titanium alloys |
US9777361B2 (en) | 2013-03-15 | 2017-10-03 | Ati Properties Llc | Thermomechanical processing of alpha-beta titanium alloys |
US9869003B2 (en) | 2013-02-26 | 2018-01-16 | Ati Properties Llc | Methods for processing alloys |
US10053758B2 (en) | 2010-01-22 | 2018-08-21 | Ati Properties Llc | Production of high strength titanium |
US10094003B2 (en) | 2015-01-12 | 2018-10-09 | Ati Properties Llc | Titanium alloy |
US10502252B2 (en) | 2015-11-23 | 2019-12-10 | Ati Properties Llc | Processing of alpha-beta titanium alloys |
US10513755B2 (en) | 2010-09-23 | 2019-12-24 | Ati Properties Llc | High strength alpha/beta titanium alloy fasteners and fastener stock |
US11111552B2 (en) | 2013-11-12 | 2021-09-07 | Ati Properties Llc | Methods for processing metal alloys |
Families Citing this family (37)
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FR2772790B1 (fr) * | 1997-12-18 | 2000-02-04 | Snecma | ALLIAGES INTERMETALLIQUES A BASE DE TITANE DU TYPE Ti2AlNb A HAUTE LIMITE D'ELASTICITE ET FORTE RESISTANCE AU FLUAGE |
US6767418B1 (en) * | 1999-04-23 | 2004-07-27 | Terumo Kabushiki Kaisha | Ti-Zr type alloy and medical appliance formed thereof |
EP1114876B1 (de) * | 1999-06-11 | 2006-08-23 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Titanlegierung und verfahren zu deren herstellung |
US6402859B1 (en) | 1999-09-10 | 2002-06-11 | Terumo Corporation | β-titanium alloy wire, method for its production and medical instruments made by said β-titanium alloy wire |
WO2001083838A1 (fr) * | 2000-05-02 | 2001-11-08 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Alliage de titane |
JP4547797B2 (ja) * | 2000-12-19 | 2010-09-22 | 大同特殊鋼株式会社 | 生体用Ti合金およびその製造方法 |
DE60138731D1 (de) | 2000-12-20 | 2009-06-25 | Toyota Chuo Kenkyusho Kk | Verfahren zur Herstellung einer TITANLEGIERUNG MIT HOHEM ELASTISCHEM VERFORMUNGSVERMÖGEN. |
EP1375690B1 (de) * | 2001-03-26 | 2006-03-15 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Hochfeste titanlegierung und verfahren zu ihrer herstellung |
US20030220696A1 (en) * | 2002-05-23 | 2003-11-27 | Levine David Jerome | Implantable porous metal |
JP4257581B2 (ja) * | 2002-09-20 | 2009-04-22 | 株式会社豊田中央研究所 | チタン合金およびその製造方法 |
US20070276488A1 (en) * | 2003-02-10 | 2007-11-29 | Jurgen Wachter | Medical implant or device |
DE10305349A1 (de) | 2003-02-10 | 2004-08-26 | Cell Center Cologne Gmbh | Innenohr-Steckverbindung |
ATE343403T1 (de) * | 2003-02-10 | 2006-11-15 | Heraeus Gmbh W C | Verbesserte metalllegierung für medizinische geräte und implantate |
US20080038146A1 (en) * | 2003-02-10 | 2008-02-14 | Jurgen Wachter | Metal alloy for medical devices and implants |
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US7722805B2 (en) * | 2003-12-25 | 2010-05-25 | Institute Of Metal Research Chinese Academy Of Sciences | Titanium alloy with extra-low modulus and superelasticity and its producing method and processing thereof |
CN1323181C (zh) * | 2004-04-29 | 2007-06-27 | 大连盛辉钛业有限公司 | 一种高强度低模量生物医用钛合金 |
DE102004022458B4 (de) * | 2004-04-29 | 2006-01-19 | Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. | Kaltumformbare Formkörper aus Titanbasislegierungen und Verfahren zu deren Herstellung |
DE102006025292A1 (de) * | 2006-05-31 | 2007-12-06 | Gfe Metalle Und Materialien Gmbh | Biokompatible Titanlegierung, Verfahren zu deren Herstellung sowie daraus bestehendes medizinisches Knochen-Implantat |
EP2297370B1 (de) * | 2008-05-28 | 2013-12-04 | Korea Institute Of Machinery & Materials | Titanlegierung auf beta-basis mit niedrigem elastizitätsmodul |
EP2301590B1 (de) | 2008-06-03 | 2014-10-29 | Advanced Medix Inc. | Verfahren zur herstelung eines knochenreparaturmaterials |
EP2364376A1 (de) | 2008-09-23 | 2011-09-14 | Sandvik Intellectual Property AB | Titanlegierung |
US8639352B2 (en) * | 2009-04-06 | 2014-01-28 | Medtronic, Inc. | Wire configuration and method of making for an implantable medical apparatus |
US8613818B2 (en) | 2010-09-15 | 2013-12-24 | Ati Properties, Inc. | Processing routes for titanium and titanium alloys |
US8340759B2 (en) | 2011-04-22 | 2012-12-25 | Medtronic, Inc. | Large-pitch coil configurations for a medical device |
US8660662B2 (en) | 2011-04-22 | 2014-02-25 | Medtronic, Inc. | Low impedance, low modulus wire configurations for a medical device |
US9409008B2 (en) | 2011-04-22 | 2016-08-09 | Medtronic, Inc. | Cable configurations for a medical device |
WO2013016523A1 (en) * | 2011-07-28 | 2013-01-31 | Synthes Usa, Llc | Orthopedic implants |
RU2485197C1 (ru) * | 2011-10-03 | 2013-06-20 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" | Металлический наноструктурный сплав на основе титана и способ его обработки |
KR101234505B1 (ko) | 2012-11-08 | 2013-02-20 | 한국기계연구원 | 선형적 탄성변형을 하며 초고강도, 초저탄성 특성을 가지는 타이타늄 합금 |
CN103074511B (zh) * | 2012-11-13 | 2015-07-22 | 西北有色金属研究院 | 一种医用多孔植入合金材料及其制备方法 |
US20140212688A1 (en) * | 2013-01-31 | 2014-07-31 | Ametek, Inc. | High grade titanium alloy sheet and method of making same |
WO2017003192A1 (ko) * | 2015-06-30 | 2017-01-05 | (주)강앤박메디컬 | TiNi계 의료용 합금 및 그 제조 방법 |
CN105400990B (zh) * | 2015-07-30 | 2017-10-31 | 贵州大学 | 一种低模量高强度生物医用钛合金及其制备方法 |
FR3047489B1 (fr) * | 2016-02-08 | 2022-09-23 | Abdelmadjid Djemai | Procede de fabrication d'un beta-alliage titane niobium zirconium (tnz) a tres bas module d'elasticite pour applications biomedicales et son mode de realisation par fabrication additive |
PT3489375T (pt) | 2017-11-22 | 2020-07-14 | Biotech Dental | Ligas ternárias de ti-zr-o, métodos para a produção das mesmas e utilizações associadas das mesmas |
BR112020019365A2 (pt) | 2018-04-13 | 2020-12-29 | Taniobis Gmbh | Pó de metal para impressão em 3d |
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-
1995
- 1995-10-04 AU AU33057/95A patent/AU705336B2/en not_active Ceased
- 1995-10-05 CA CA002159974A patent/CA2159974A1/en not_active Abandoned
- 1995-10-13 DE DE69507104T patent/DE69507104T2/de not_active Expired - Fee Related
- 1995-10-13 EP EP95307277A patent/EP0707085B1/de not_active Expired - Lifetime
- 1995-10-16 JP JP7293730A patent/JPH08299428A/ja active Pending
-
1997
- 1997-01-31 US US08/792,091 patent/US5871595A/en not_active Expired - Fee Related
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US8048240B2 (en) | 2003-05-09 | 2011-11-01 | Ati Properties, Inc. | Processing of titanium-aluminum-vanadium alloys and products made thereby |
US9796005B2 (en) | 2003-05-09 | 2017-10-24 | Ati Properties Llc | Processing of titanium-aluminum-vanadium alloys and products made thereby |
US8597443B2 (en) | 2003-05-09 | 2013-12-03 | Ati Properties, Inc. | Processing of titanium-aluminum-vanadium alloys and products made thereby |
US8597442B2 (en) | 2003-05-09 | 2013-12-03 | Ati Properties, Inc. | Processing of titanium-aluminum-vanadium alloys and products of made thereby |
US8623155B2 (en) | 2004-05-21 | 2014-01-07 | Ati Properties, Inc. | Metastable beta-titanium alloys and methods of processing the same by direct aging |
US7837812B2 (en) | 2004-05-21 | 2010-11-23 | Ati Properties, Inc. | Metastable beta-titanium alloys and methods of processing the same by direct aging |
US9523137B2 (en) | 2004-05-21 | 2016-12-20 | Ati Properties Llc | Metastable β-titanium alloys and methods of processing the same by direct aging |
US8568540B2 (en) | 2004-05-21 | 2013-10-29 | Ati Properties, Inc. | Metastable beta-titanium alloys and methods of processing the same by direct aging |
US9593395B2 (en) | 2005-09-13 | 2017-03-14 | Ati Properties Llc | Titanium alloys including increased oxygen content and exhibiting improved mechanical properties |
US8337750B2 (en) | 2005-09-13 | 2012-12-25 | Ati Properties, Inc. | Titanium alloys including increased oxygen content and exhibiting improved mechanical properties |
US7611592B2 (en) | 2006-02-23 | 2009-11-03 | Ati Properties, Inc. | Methods of beta processing titanium alloys |
US10053758B2 (en) | 2010-01-22 | 2018-08-21 | Ati Properties Llc | Production of high strength titanium |
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Also Published As
Publication number | Publication date |
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EP0707085A1 (de) | 1996-04-17 |
JPH08299428A (ja) | 1996-11-19 |
AU3305795A (en) | 1996-05-02 |
AU705336B2 (en) | 1999-05-20 |
US5871595A (en) | 1999-02-16 |
CA2159974A1 (en) | 1996-04-15 |
DE69507104T2 (de) | 1999-06-10 |
DE69507104D1 (de) | 1999-02-18 |
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